JPH0336542A - Silver halide photographic sensitive material and method for processing the same - Google Patents

Abstract

PURPOSE:To prevent deterioration of image quality due to coloring of residual dyes and the like even after ultrahigh-speed processing by incorporating 3 kinds of specified compound and a specified polymer. CONSTITUTION:Hydrophilic colloidal layers contain silver halide grains spectrally sensitized by the 3 kinds of compounds each represented by formulae I - III and at least one of the hydrophilic colloidal layer contains the polymer compound having sulfonated hetero rings. In formulae I - III, each of R1 - R6 is alkyl; each of Y1 and Y2 is a nonmetallic atomic group necessary to form a pyrrolopyridine ring; L is methine group; X is anion; m is 4 or 5; and n is 1 or 2, thus permitting coloring due to residual dyes to be reduced and not unevenly colored even when ultrahigh-speed processing is conducted within a processing time of 45sec using a developing, fixing and rinsing solutions.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for forming an image on a silver halide photographic light-sensitive material, and more particularly to a method for forming an image on a printed light-sensitive material suitable for rapid processing.

[Conventional technology]

In recent years, the consumption of silver halide photographic materials has continued to increase. For this reason, the number of sheets of silver halide photographic light-sensitive materials being processed has increased, and there is a demand for speeding up the development process, that is, increasing the amount of processing within the same amount of time.

The above trend can also be seen in the printing plate making field.

In other words, as the immediacy and number of times information is rapidly increasing, it has become necessary to perform printing plate-making work in a short delivery time and in larger quantities. In order to meet such demands of the printing plate making industry, it is necessary to promote the simplification of the printing process and to process printing plate making films more quickly.

However, shortening the processing time is not preferable because it causes deterioration of residual color and unevenness of residual color.

[Purpose of the invention]

In order to solve the above-mentioned problems, the purpose of the present invention is to provide good residual color even when performing ultra-quick processing in which processing time for development, fixing, washing, and/or stabilizing liquid is within 45 seconds. An object of the present invention is to provide a method for processing a silver halide photographic material that is uniform and has excellent antistatic performance.

[Structure of the invention]

The above-mentioned object of the present invention is to provide a silver halide photographic material comprising a support and a hydrophilic colloid layer coated on the support and comprising at least one silver halide emulsion layer. The silver halide grains contained in the hydrophilic colloid layer are spectrally sensitized by compounds represented by the following formulas (Ia), (Ib) and -Ic, and the at least one hydrophilic colloid layer contains sulfonic acid groups. A silver halide photographic light-sensitive material characterized by containing a polymer compound having a heterocycle substituted with This is achieved by a method for processing a silver halide photographic material, which is characterized in that the processing time is 45 seconds or less.

General formula (Ia) General formula (Ib) (X)n-+ General formula [Ic] [In the formula, RIRx, R3, R1RI and R each represent an alkyl group, and Yl and Y2 form a pyrrolopyridine ring represents a group of nonmetallic atoms necessary for , and is included in the ring of Y.

R IR! in general formula (Ia) , R3, R4, Rs
,R1Y,,Y! , -R in soft form (1'b)
t, Rx, R3, R4°Rs, RsiY leY ff
i and - RoRt, Rs, Rt in soft [Ic],
Rs, Rs, Y, Ys are each a group that allows the dye molecule to have at least two acid groups or -CH!
Ct(! Represents a group that allows at least two substituents to have one or more OR groups.

R represents a hydrogen atom or an alkyl group.

L represents a methine group, and Xe represents an anion.

m represents an integer of 4 to 5, and n represents an integer of 1 or 2.

When the dye forms an inner salt, n is 1. ] The present invention will be explained in detail below.

The processing time in the developing, fixing, washing and/or stabilizing solution of the present invention is 45 seconds or less, which means that the leading edge of the film enters the developing solution and then comes out of the fixing solution, washing solution and/or stabilizing solution. The time required for this is 45 seconds or less, which includes the time from the developer to the fixer and the time from the fixer to the washing solution.

Examples of the acid group in the soft formulas (I a), [1b) and [Ic] include a sulfonic acid group, a carboxylic acid group, a phosphonic acid group, and each of these acid groups includes its salt. Examples of the salt include alkali metal salts such as sodium and potassium salts, and organic ammonium salts such as ammonium, triethylamine, and pyridine.

The alkyl group represented by Ri, Rz-Rs, R4, R6 and R6 is preferably a lower alkyl group having 1 to 8 carbon atoms (
For example, methyl, ethyl, propyl, i-7'.

(biru, butyl group, etc.), and the above acid substituent or -CH
, CH1OR group.

The alkyl group represented by R is preferably a lower alkyl group having 4 or less carbon atoms.

-CH, CH, OR group-containing substituents include, for example, hydroxyethyl group, hydroxyethoxyethyl group, methoxyethoxyethyl group, hydroxyethylcarbamoylmethyl group, hydroxyethoxyethylcarbamoylmethyl group, N,N-dihydroxyethylcarbamoylmethyl group, hydroxyethylsulfamoylethyl group, methoxyethoxyethoxycarbonylmethyl group, and the like.

Y, and Y! Other substituents that may have include sulfo groups (including salts), carboxyl groups (including salts)
, hydroxyl group, cyano group, halogen atom (e.g.
fluorine, chlorine, bromine atoms, etc.).

The methine group represented by L may also have a substituent, and examples of the substituent include substituted or unsubstituted lower alkyl groups having 1 to 5 carbon atoms (for example, methyl, ethyl, 3-hydroxyzolopyl, 2- sulfoethyl group, etc.), halogen atoms (e.g.
Examples include feroxin, chlorine, bromine atoms, etc.), aryl groups (eg, phenyl groups), and alkoxy groups (eg, methoxy, ethoxy groups, etc.). In addition, the substituents of the methine group are bonded to each other to form a 6-membered ring containing three methine groups (for example, 4,4-
dimethylcyclohexene ring).

The anion represented by xe is not particularly limited, but specific examples include a halogen ion, p-toluenesulfonate ion, and ethylsulfate ion.

The dyes represented by the soft formula [Ia], [Ib] and [Ic] used in the present invention (hereinafter referred to as the dye of the present invention)
Specific examples are shown below, but the present invention is not limited thereto.

Specific compounds (2) (3) (4) (5) (6) (7) (8) (9) (10) (11) (12) (13) (14) (15) (16) (17 ) (18) (19) (20) (21) (24) (25) (28) (29) (30) (31) (33) The dye of the present invention was published in the Journal of the Chemical Society ( J,Chen+,Soc,) 189 pages (1
It can be synthesized with reference to U.S. Pat. No. 933, No. 933, U.S. Pat.

Examples of the mother nucleus of the dye of the present invention include the following compounds.

Compound (A) is J, Che+m, Soc, 3202 (
(1959) and the method described in British Patent No. 870.753.

Compound (B) has been described in J. Chem. Soc., 584 (19
It can be synthesized by the method described in 61).

Compound (C) can be synthesized by the method described in British Patent No. 841.588.

Using these cores, quaternization, sulfonation, etc. can be performed as necessary. Or J, Chem.

Soc, 3202 (1959) and J. Chem.
Soc, ', 584 (1961) I: N-alkyl-N-pyridylhydrazine is synthesized according to the described synthesis method, cyclization reaction is performed via hydrazone, and l-alkyl substitution/ It is also possible to obtain a 3H-pyrrolopyridine derivative and use this as a starting material.

The polymer compound having a heterocycle substituted with a sulfonic acid group (hereinafter referred to as the polymer of the present invention) used in the present invention preferably has a molecular weight in the range of 2,000,000 to 2,000,000. Preferred examples of the heterocycle in the polymer of the present invention include a pyridine ring, a pyrrolidine ring, a carbazole ring, a virol ring, a thiophene ring, a furan ring, and an indole ring. Examples of the sulfonic acid group include a C1-16 alkylsulfonic acid group or a substituted alkylsulfonic acid group.

The bonding group between the sulfonic acid group and the heterocyclic group may be any divalent bonding group composed of carbon, nitrogen, sulfur, oxygen, and phosphorus atoms.

Homopolymers, copolymers, and terpolymers are listed below as typical examples of the polymer compound of the present invention, but the invention is not limited to these.

5O=Na 03Na SO,Na (6) (7) (8) (9) So,Na 5o,Na (10) (11) (12) (13) (14) (16) (17) (18) ( 21) M#600,000x:y:z:v=40:30:20:10M#500,000M=jυ force (23) x:y:z=40:30:30 Su8=, 500,000 above books As a medium for polymerizing the monomer capable of forming the inventive polymer compound, in addition to an aqueous solution, alcohol such as methanol or ethanol, a hydrophilic colloid solution matrix such as an aqueous gelatin solution, or tricresyl phosphate sodium salt, Polymers can be formed using the above polymerization initiators in high boiling point solvents such as liquid paraffin.

The amount of these compounds added is 10-'~lo'mg/m"
Up to 10-! is preferred, particularly 10-! ~lO'mg
It is.

The polymer compound of the present invention can be easily made into synthetic leather by obtaining a monomer capable of forming a polymer as a commercially available chemical product.

The silver halide photographic material of the present invention comprises a support and a hydrophilic colloid layer containing at least one silver halide emulsion layer coated on the support, and this silver halide emulsion is directly coated on the support. Alternatively, it may be coated via a hydrophilic colloid layer containing no silver halide emulsion, and a hydrophilic colloid layer may be further coated as a protective layer on the silver halide emulsion layer. The silver halide emulsion layer may also be divided into silver halide emulsion layers of different sensitivities, eg high and low sensitivity. In this case, the silver halide emulsion layer may be provided with an intermediate layer of a hydrophilic colloid layer between these layers, or an intermediate layer may be provided between the silver halide emulsion layer and the protective layer. good. General formula CI a), [: I
b), [: I The layer containing the compound of c) and the polymer of the present invention is a hydrophilic colloid layer, preferably a silver halide emulsion layer and/or a hydrophilic colloid adjacent to the silver halide emulsion layer. It is a layer.

In order to incorporate the polymer of the present invention into the hydrophilic colloid layer, the polymer of the present invention may be dissolved in appropriate water and/or an organic solvent and then added, or the solution dissolved in an organic solvent may be added to gelatin or a hydrophilic gelatin derivative. Examples include a method in which the compound is added after being dispersed in a sex colloid matrix, or a method in which the compound is added after being dispersed in latex.

The silver halide emulsion used in the light-sensitive material of the present invention includes conventional silver halide emulsions such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, and silver chloroiodobromide. Any used material can be used, but it is preferable that it contains silver chloride in an amount of 50 mol% or more, and the particle size is 0.2 μm or more.
．． The thickness is preferably 5 μm or less.

In addition, the amount of gelatin on the emulsion layer side is 2.89/m” or less,
Preferably it is 2-5y/m'' or less.

The silver halide grains may be obtained by any of the acid method, neutral method, and ammonia method.

Silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside and surface layer of the grain, and the latent image is mainly on the surface. It may be a particle that is formed inside the particle, or it may be a particle that is mainly formed inside the particle.

Any shape of the silver halide grains according to the present invention can be used. One preferred example is a cube having a (100) plane as a crystal surface.

Also, U.S. Patent Nos. 4,183.756 and 4,225,6
No. 66, JP-A-55-26589, JP-A-55-42
737, etc., and The Journal of Photographic Science (J-, PhoLgr, s
Particles having shapes such as octahedrons, tetradecahedrons, and dodecahedrons can be prepared by the method described in literatures such as Ci), 21.39 (1973), and used. Furthermore, particles having twin planes may be used.

The silver halide grains according to the present invention may be of a single shape or may be a mixture of grains of various shapes.

Also, any grain size distribution may be used, and emulsions with a wide grain size distribution (referred to as polydisperse emulsions) may be used, or emulsions with a narrow grain size distribution (referred to as monodisperse emulsions) may be used. They may be used alone or in combination. or,
A polydisperse emulsion and a monodisperse emulsion may be mixed and used.

The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions.

In the present invention, monodisperse emulsions are preferred. As monodisperse silver halide grains in a monodisperse emulsion, the weight of silver halide contained within a grain size range of ±20% around the average grain size r is 60% or more of the weight of all silver halide grains. A certain amount is preferable, particularly preferably 70% or more, and still more preferably 80% or more.

Here, the average particle size T is the frequency ni of particles having particle size ri
Define the grain size ri when the product of niX ri and i3 becomes maximum.

(3 significant digits, round off the smallest digit.) The grain size here refers to the diameter in the case of spherical silver halide grains, and the projected image in the case of grains with shapes other than spherical. This is the diameter when the circumferential area is converted into a circular image.

The particle size can be obtained, for example, by photographing the particles with an electron microscope at a magnification of 10,000 to 50,000 times, and actually measuring the particle diameter or projected area on the print.

(The number of grains to be measured is indiscriminately 100 or more.) Particularly preferred highly monodisperse emulsions of the present invention have a monodispersity of 20 or less, more preferably 15 or less. be.

Here, the average particle diameter and particle diameter standard deviation shall be determined from ri defined above. Monodisperse emulsion is disclosed in Japanese Patent Application Laid-Open No. 54-4852.
No. 1, No. 58-49938 and No. 60-122935
This information can be obtained by referring to the Publication No.

The photosensitive silver halide emulsion can be used as a so-called unripe emulsion (Pr1m1tive) without chemical sensitization, but it is usually used as an unripe emulsion. Sensitized.

For chemical sensitization, the Glafkides or Z
The book by Elikuian et al. or H. Fr1eser
Edited by De Grundlagen der Fotografisien Prozesse Mido Zilber Halogenite 7 (Di
e Grundlagen der Photogra
phischen Prozesse 1Ilit S
ilberhalogenidenx＾kademic
che Verlagsgesellschaft,
(1968) can be used.

That is, a sulfur sensitization method using a sulfur-containing compound capable of reacting with silver ions or active gelatin, a reduction sensitization method using a reducing substance, and gold or other noble metal compounds can be used.

Further, there are no particular restrictions on conditions such as pH% pAgs temperature during chemical sensitization, but the pH value is preferably 4 to 9, particularly 5 to 8, and the pAg value is 5 to 11. In particular, it is preferable to keep it between 7 and 9. Also, the temperature is 40 to 90°C, especially 4
5-75°C is preferred.

In addition to the aforementioned sulfur sensitization and gold/sulfur sensitization, the photographic emulsion used in the present invention can also be subjected to reduction sensitization using a reducing substance, noble metal sensitization using a noble metal compound, or the like.

As the photosensitive emulsion, the above emulsion may be used alone,
Two or more emulsions may be mixed.

When carrying out the present invention, for example, 4-hydroxy-6-methyl-1,3,
Various stabilizers can also be used, including 3a,7-tetrazaindene, 5-mercapto-1-phenyltetrazole, and the like.

Furthermore, if necessary, a silver 10 genide solvent such as a thioether, or a crystal habit control agent such as a mercapto group-containing compound or a sensitizing dye may be used.

The /% silver halide grains used in the emulsion of the present invention are formed by forming cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts, rhodium salts or complex salts, Metal ions can be added using iron salts or complex salts to be included inside the particles and/or on the particle surface.

In the emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may be left contained. In the case of removing the salts, it can be carried out based on the method described in Research Disclosure No. 17643.

In the silver halide photographic material according to the present invention, a sensitizing dye may be further added and used in combination.

The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, hemioxanol dyes, and the like.

The sensitizing dye used in the present invention is used at a concentration equivalent to that used for ordinary negative-working silver 10 genide.

In particular, it is advantageous to use the dye at a concentration that does not substantially reduce the inherent sensitivity of the silver halide emulsion.

Approximately 1.0% of sensitizing dye per mole of silver halide. OX 10"
~5 X 10-' moles of sensitizing dye are preferred, especially about 4 X 10-' to 2 X moles of sensitizing dye per mole of silver halide.
Preferably, a concentration of 10-' molar is used.

The sensitizing dyes of the present invention can be used alone or in combination of two or more. The sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used, especially for the purpose of supersensitization.

The silver halide photographic material according to the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation and extrusion. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, azo dyes, and the like. Among them, oxanol dyes; hemioxanol dyes and merocyanine dyes are useful.

In the silver halide photographic material according to the present invention, when dyes, ultraviolet absorbers, etc. are included in the hydrophilic colloid layer, they may be mordanted with a cationic polymer or the like.

Various compounds can be added to the above photographic emulsion in order to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage or processing of the silver halide photographic light-sensitive material.

Further, the silver halide photographic light-sensitive material of the present invention has U.S. Pat. No. 3,411,911 and U.S. Pat.
12, Japanese Patent Publication No. 45-5331, etc., may be included.

The photosensitive material of the present invention may further contain various additives depending on the purpose. These additives are described in more detail in Research Disclosure Vol. 176, 1 tem.
17643 (December 1978) and Volume 187 ■
tea18716 (November 1979), and the additive types 1. Chemical sensitizer 2, sensitivity enhancer RD 17643 23 pages RD 18716 648 pages Right column Same as above 4, Brightener 24 pages Anti-stinting agent Dye image stabilizer Hardener Binder Plasticizer/lubricant Coating aid/Surface active agent Static inhibitor Page 25 Right column Page 25 Page 26 Page 26 Page 26-27 Pages 27 Page 650 Page Left to right column Page 651 Left column Same as above 650 Right column Same as above Same as above In carrying out the silver halide photographic light-sensitive material of the present invention, For example, the emulsion layer and other layers can be constructed by coating on one or both sides of a flexible support commonly used in photographic materials. Useful flexible supports include films made of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate and acetate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or α- Olefin polymer (
Examples include paper coated with or laminated with polyethylene, polypropylene, ethylene/butene copolymer, or the like. The support may be colored using dyes or pigments. It may be made black for the purpose of blocking light. The surface of these supports is generally treated with an undercoat to improve adhesion with emulsion layers and the like. The undercoating treatment is as per JP-A-52-104913 and JP-A-52-104913.
No. 9-18949, No. 59/19940, No. 59-1
The treatments described in each publication of No. 8949 are preferred.

The surface of the support may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment.

In the silver halide photographic light-sensitive material according to the present invention, the photographic emulsion layer and other hydrophilic colloid layers can be coated on the support or other counterfeit by various coating methods. For coating, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, etc. can be used.

The development time in the present invention is within 20 seconds, preferably 15 seconds.
Describe the development, fixing, washing, and drying processes that take less than seconds.

The developing agent used in the black and white developer used in the present invention has dihydroxybenzene chains and l-
Most preferred is a combination of 7enyl-3-pyrazolidones. Of course, a p-aminophenol type developing agent may also be included.

Examples of dihydroxybenzene developing agents used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2. S-
, chlorohydroquinone, 2,3-dibromohydroquinone, 2,5-dimethylhydroquinone, etc., with hydroquinone being particularly preferred.

As the developing agent for l-phenyl-3-pyrazolidone or its derivative used in the present invention, l-phenyl-4,4-dimethyl-3-pyrazolidone, l-7enyl-4-methyl-4-hydroxymethyl-3-pyrazolidone , 1-7enyl-4,4-dihydroxymethyl-3-pyrazolidone, and the like.

The p-aminophenol developing agents used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N-(β-hydroxyethyl)-p-aminophenol, and N-(4-hydroxyphenyl)glycine. , 2-methyl-p-aminophenol, p-benzylaminophenol, etc. Among them, N-methyl-p-
Aminophenols are preferred.

The developing agent is preferably used in an amount of usually 0.01 mol/ff-1.2 mol/Q.

Preservatives for sulfite used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite,
Examples include formaldehyde sodium binitate. The amount of sulfite is preferably 0.2 mol/I2 or more, particularly 0.4 mol/Q or more. Further, the upper limit is preferably 2.5 mol/Q.

The pH of the developer used in the present invention is preferably in the range of 9 to 13. More preferably, the pH range is from 1o to 12.

Alkaline agents used to set pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, trisodium phosphate, and potassium triphosphate.
Contains H regulator.

JP-A-61-28708 (borates), JP-A-60-
Buffers such as No. 93439 (e.g., sucrose, acetoxime, 5-sulfosalcylic acid), phosphates, carbonates, etc. may also be used.

Additives used in addition to the above components include development inhibitors such as sodium bromide, potassium bromide, and potassium iodide:
Organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, nitinol, methanol; l-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, etc. It may contain antifoggants such as mercapto compounds, indazole compounds such as 5-nitroindazole, and benztriazole compounds such as 5-methylbenztriazole, and may further contain color toning agents, surfactants, and antifoaming agents as necessary. , hard water softener, JP-A-1987-
It may also contain the amino compounds described in No. 106244.

In the present invention, silver stain preventive agents such as the compounds described in JP-A-56-24347 can be used in the developer.

In the developer of the present invention, amino compounds such as alkanolamines described in JP-A-56-106244 can be used.

In addition, "Photographic Processing Chemistry" by F. A. Messon, published by Focal Press (1
No. 966, pp. 226-229, U.S. Pat.
．． No. 015, No. 2,592.364, Japanese Unexamined Patent Publication No. 1973-6
Those described in No. 4933 may also be used.

In the present invention, "development time" and "fixing time" respectively mean
The time from when the photosensitive material to be processed is immersed in the developing tank solution of the automatic processing machine until it is immersed in the next fixing solution, and the time from when it is immersed in the fixing tank solution until it is immersed in the next washing tank solution (stabilizing solution). say the time

Further, "washing time" refers to the time during which the product is immersed in the washing tank liquid.

Furthermore, "drying time" refers to a drying zone where the automatic processing machine is equipped with a drying zone where hot air is normally blown at 35°C to 100°C, preferably 40°C to 80°C. refers to time.

The development temperature and time are about 25°C to 50°C for 15 seconds or less, preferably 30°C to 40°C for 6 seconds to 15 seconds.

The fixer is an aqueous solution containing thiosulfate and has a pH of 3.8 or higher, preferably 4.2 to 5.5.

Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, which contain thiosulfate ions and ammonium ions as essential components, and ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed. The amount of the fixing agent used can be changed as appropriate, and is generally about 0.1 to about 6 mol/Q.

The fixer may also contain water-soluble aluminum salts that act as hardeners, such as aluminum chloride, ammonium sulfate, potassium alum, and the like.

The fixing solution may include tartaric acid, citric acid, or conductors thereof alone or in combination of two or more thereof.

Those containing 0.005 mol or more of these compounds per 1Q of the fixing solution are effective, and 0.01 to 0.03 mol/Q is particularly effective.

Specifically, the fixing solution includes tartaric acid, potassium tartrate, sodium tartrate, potassium sodium tartrate, citric acid, sodium citrate, potassium citrate, lithium citrate, ammonium citrate, etc. If desired, a preservative (e.g. , sulfites, bisulfites), pH buffers (
(e.g., acetic acid, nitric acid), pH adjusters (e.g., sulfuric acid),
Chelating agent with hard water softening ability and patent application No. 60-21356
The compound described in No. 2 can be included.

The fixing temperature and time are preferably 6 seconds to 1 minute at about 0°C to about 50°C, more preferably 6 seconds to 30 seconds at 30°C to 40°C, and even more preferably 6 seconds at 30°C to 40°C. ~15 seconds.

Where the fixer concentrate is replenished into the automatic processor in the method of the invention with water to dilute it as the light-sensitive material is processed, it is most preferred that the fixer concentrate is comprised of an l-agent. is the same as for the developer.

The fixer solution can exist stably as a l agent at pH 4,
5 or more, more preferably pH 4.65 or more. This is because if the pH is less than 4.5, the thiosulfate will decompose and eventually become sulfurized, especially if the fixer is left for a long period of time until it is actually used.

Therefore, when the pH is in the range of 4.5 or higher, less sulfur dioxide gas is generated, which improves the working environment. The upper limit of po is not so strict, but if it is fixed at too high a pH, the pH of the membrane will be high even after washing with water, the membrane will swell, and the drying load will increase, so the upper limit is around pH 7. Fixing solutions that use aluminum salts to harden films have a pH limit of 5.5 to prevent precipitation of aluminum salts.

In the present invention, either the developing solution or the fixing solution may be a so-called working solution that does not require dilution water as described above (that is, it is replenished as an undiluted solution).

The amount of each concentrate supplied to the processing tank liquid and the mixing ratio with dilution water can be varied depending on the composition of the concentrate, but generally the ratio of concentrate to dilution water is 1 to 8. The total amount of each of these developing solutions and fixing solutions is the same as the photosensitive material 1. % is preferably from 50 m12 to 1500 nff.

In the present invention, the photosensitive material is subjected to water washing or stabilization treatment after being developed and fixed.

Any method known in the art can be applied to the washing or stabilization treatment, and water containing various additives known in the art can also be used as the washing water or stabilizing liquid. By using anti-mold water as washing water or stabilizing liquid, not only is it possible to save water by reducing the amount of replenishment to less than 3Q per liter of photosensitive material, but it also eliminates the need for piping for installing an automatic processing machine. Furthermore, the number of stock tanks can be reduced. That is, the solution dilution water and washing water or stabilizing solution for the developer and fixer can be supplied from a common single layer stock tank, making it possible to further downsize the automatic developing machine.

If anti-mildew water is used in combination with the washing water or stabilizing liquid, the formation of lime scale can be effectively prevented.
It is possible to save 0 to 112 liters of water per unit, preferably 0 to 112 liters.

Here, when the replenishment amount is O, there is no replenishment at all except for appropriately replenishing the amount of washing water in the washing tank that has decreased due to natural evaporation, etc. In other words, the so-called "reservoir water" is essentially not refilled. Refers to cases in which a processing method is used.

As a method of reducing the amount of replenishment, a multistage countercurrent system (for example, two stages, three stages, etc.) has been known for a long time. If this multi-stage countercurrent method is applied to the present invention, the photosensitive material in the fixer will be processed in a progressively cleaner direction, that is, in sequential contact with the processing solution that is not contaminated with the fixer, resulting in even more efficient processing. Washing is done. According to this, unstable thiosulfates and the like are appropriately removed, the possibility of discoloration and fading is further reduced, and an even more significant stabilizing effect can be obtained. The amount of water used for washing is also much smaller compared to conventional methods.

When washing with a small amount of water, patent application 1729/1986
It is more preferable to provide a squeeze roller cleaning tank as described in No. 68.

Further, part or all of the overflow liquid from the washing or stabilizing bath, which is generated by replenishing the washing or stabilizing bath with anti-mold water depending on the treatment, is disclosed in Japanese Patent Application Laid-Open No. 60-23
As described in Japanese Patent Application No. 5133, it can also be used in a processing liquid having a fixing ability, which is a processing step before that. This is more preferable because the stock water can be saved and the amount of waste liquid can be reduced.

Anti-mildew methods include the ultraviolet irradiation method described in JP-A No. 60-263939, the method using a magnetic field described in JP-A No. 60-263940, and the use of ion exchange resin described in JP-A No. 61-131632. How to make pure water, patent application 1986
-253807, 60-295894, 61-
A method using a fungicide described in No. 63030'5-1 No. 6151396 can be used.

Furthermore, L, E, West Water Quali
t,y Cr1teria"Photo Sci
& Eng, Vol. 9 No. 6 (1965),
M, W, Be-ach Microbiologic
al Growths in Motion-P
ic-cure Processing”SMP
TE Journal Vol, 85. (1976
).

R. O. Deegan, “Photo Pro
cessing Wash Water Bioci
des' J, In+aging Tech, Vol.
10. No. 6 (1984) and JP-A-57-8542
No. 57-58143, No. 58-105145,
No. 57-132146, No. 58-18631, No. 5
Antibacterial agents, anti-inflammatory agents, surfactants, etc. described in No. 7-97530 and No. 57-157244 can also be used in combination.

Furthermore, for the washing bath, R.T. Kreiman J.Ima
RESEARCH, an inthiazoline compound described in GE, Techlo, (6) 242 (1984)
DISCLOSURE Volume 205, l Lem2052
6 (May 1981), isothiazoline compounds described in Volume 228, Item 22845 (
Inthiazoline compounds described in Japanese Patent Application No. 1983-51396, etc. can also be used together as microbiocides.

Furthermore, specific examples of anti-piping agents include phenol, 4-chlorophenol, pentachlorophenol, cresol,
o-7 Dynylphenol, chlorophene, dichlorophene, formaldehyde, geltaraldehyde, chloracetamide, p-hydroxybenzoic acid ester, 2-
(4-Thiazoline)-benzimidazole, benzisothiazolin-3-one, dodecyl-benzyl-dimethylammonium-chloride, N-(fluorodichloromethylthio)-7talimide, 2.4.4', trichloro-2'-hydroxy diphenyl ether, etc.

The water stored in the water stock tank after being treated with anti-mold means is mixed with water used to dilute the undiluted solution of the processing solution such as the developer fixer, and the amount thereof added is preferably 0.01 to log/(2, more preferably O1
1 to 5 g/12.

Furthermore, in addition to the silver image stabilizer, various surfactants can be added to the washing water for the purpose of preventing water droplet unevenness. As the surfactant, any of cationic, anionic, nonionic, and amphoteric types may be used. Specific examples of surfactants include compounds described in "Surfactant Handbook" published by Kogaku Tosho Co., Ltd.

Various compounds are added to the stabilizing bath for the purpose of stabilizing the image. For example, adjusting the membrane pH (e.g. pH 3
~8) various buffering agents (e.g. borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid) In addition to formalin, chelating agents, bactericidal agents (thiazole-based, inthiazole-based, halogenated phenols, sulfanilamide, benzotriazole, etc.), surfactants, optical brighteners, and dura mater. Various additives such as additives may be used, and two or more compounds for the same or different purposes may be used in combination.

In addition, ammonium chloride,
It is preferable to add various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate in order to improve image storage stability.

Water washing or stabilization bath temperature and time by the above method is 01
Preferably 6 seconds to 1 minute at ~50℃, but 6 seconds to 1 minute at 151-40℃
More preferably from seconds to 30 seconds, more preferably from 15°C to 40'
C! 6 seconds to 15 seconds is preferable.

According to the method of the present invention, the developed, fixed and washed photographic material is dried by squeezing out the washing water, that is, by using a squeeze roller method. Drying is carried out at a temperature of about 40'C to about 100°C, and the drying time can be changed appropriately depending on the surrounding conditions, but usually it is about 5 seconds to 1 minute, but more preferably 40'C to about 100C.
It is about 5 seconds to 30 seconds at 0'O to 80'O.

In the present invention, an even more excellent effect is exhibited in that the lower the swelling percentage of the photosensitive material, the shorter the drying time thereof.

According to the method of the present invention, the so-called dry-to-dry processing time for development, fixing, washing, and drying is within 100 seconds, preferably within 60 seconds, and more preferably within 5 seconds.
It is to be processed within 0 seconds.

Here, "dry to dry" means that from the moment the leading edge of the photosensitive material to be processed enters the film insertion area of the automatic processing machine,
This refers to the time from when the tip is processed to the moment when the tip comes out of the processor.

〔Example〕

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

Example 1 (Preparation of coating solution for back lower layer) After dissolving 500 g of gelatin in 8a water, 120 g/m'' of the dye of the present invention and 19/m'' of the polymer compound were added in Table-1.
In addition, 20g of saponin was added as a surfactant, 1g of bis-(2-ethylhexyl)sulfosuccinate sodium salt, 2g of a copolymer of butyl acrylate and vinylidene chloride as a polymer latex.
It was prepared by adding 2.5 g of styrene-maleic anhydride copolymer as a thickener and 2 g of glyoxal as a hardening agent.

(Preparation of coating solution for back upper layer) After dissolving 400 g of gelatin in 600 mff of water, 20 g of polymethyl methacrylate with an average particle size of 4 μm as a matting agent, 1 bis-(2-ethylhexyl) sulfosuccinate sodium salt as a surfactant. It was prepared by adding 3g.

(Preparation of coating solution for emulsion layer) In a container heated to 40'O containing gelatin, sodium chloride, and water, an aqueous silver nitrate solution and 2 x 10-' moles of hexachloroiridium per mole of silver halide were added. Hydrochloric acid potassium salt and a mixed aqueous solution of potassium bromide and sodium chloride to which 4 x 10-' moles of hexabromolodic acid potassium salt had been added were added by a double jet method to produce chlorobromide containing 35 mol% silver bromide. Silver particles (width of distribution 9%)
, cubic crystal grain size o, 25 μm) at pH 3,0pAg7.
The pH was adjusted to 5.7, and after returning the pH to 5.9, it was desalted using a conventional method.

This emulsion was sensitized with gold and sulfur, 60 mg of sensitizing dye (a) was added per mole of silver halide, and 70,119 mg of l-phenyl-5-mercaptotetrazole was added per mole of silver halide. 4-hydroxy-6-methyl-1,
After adding 1.2 g of 3,3a,7-tetrazaindene and gelatin to stop the ripening, further added 49 g of hydroquinone, 3 g of potassium bromide, 5 g of saponin, and styrene per mole of silver halide. - Added 2 g of maleic acid polymer, 39 g of polymer latex of acrylic and ethyl phosphate, and l-hydroxy-3,5 as a hardening agent.
It was prepared by adding dichlorotriazine sodium salt and formalin.

Sensitizing dye Ca) ■θ (Preparation of coating solution for protective layer) Add potassium bromide 109.1- to an aqueous solution of gelatin 5009.
Decyl-2-(3-impentyl)succinate-2-
It was prepared by adding 4 g of sodium sulfonate and dispersing 1009 particles of amorphous silica having an average particle size of 5 μm.

Using the above coating solution, the lower and upper layers on the back side were simultaneously coated on a polyethylene terephthalate film base with a thickness of 100 µm to which an underlayer had been applied, and then an emulsion and a protective layer were applied on the side opposite to the back layer. Coated in multiple layers at the same time. Coating Ag
The amount is 3-8g/m", and the amount of gelatin applied is 1.8g for the emulsion layer.
/m', the protective layer is 1. The upper and lower layers on the back surface were as shown in Table 1.

The thus obtained sample was processed in a conventional roller type automatic developing machine under the following conditions using the following soft developing solution and fixing solution, and residual color was evaluated.

Further, the surface resistivity of each sample was evaluated under the conditions of 23° C. and 30% RH.

Incidentally, residual color is evaluated in 10 levels, with 1o being the best, 1 to 4 being unusable, and 5 or higher being usable.

From Table 1, it can be seen that the products of the present invention have good residual color.

(Development processing conditions) (Process) (IL degree) (Time) Development 35°C
11 Arrive at sand room 34℃
11 Sand water washing Room temperature 12 Sand grain drying
50°C 10 seconds Developer recipe Pure water (ion exchange water) 800+aQ ethylenediaminetetraacetic acid disodium salt 2g Diethylene glycol 25g Potassium sulfite (55%/V aqueous solution) 60g Potassium carbonate
15g hydroquinone
20g 5-methylbenzotriazole
300 rpm 1-phenyl-5-mercaptotetrazole 0 mg 1-phenyl-5-4,4-dimethyl-3-pyrazolidinone 00 mg Potassium bromide 3.5 g Add pure water to make if. The developer pH was 10.8.

Fixer formulation (composition A) Ammonium thiosulfate <72.5% W/V aqueous solution) 40
m12 Sodium sulfite 17g Sodium acetate trihydrate 6.5g Boric acid
6g Sodium citrate dihydrate
2g acetic acid (90% w/v aqueous solution)
13.6mc (composition B) Pure water (ion exchange water) 17n+Q sulfuric acid (50% v/v aqueous solution) 4.7g aluminum sulfate (AQ, aqueous solution with 0. conversion content of 8.1% w/v) 26
．． 5g of the above composition A and composition B in 500ml of water for use as a fixer.
It was dissolved in the following order and finished to 1Q and used. [Effects of the Invention] According to the present invention, it has been possible to provide a method for processing a silver halide photographic light-sensitive material that does not cause deterioration in image quality due to residual color etc. even when ultra-rapid processing is performed.

Claims (2)

[Claims] (1) In a silver halide photographic material having a support and a hydrophilic colloid layer coated on the support and including at least one silver halide emulsion layer, halogenated in the hydrophilic colloid layer. Silver particles have the following general formula [I
a], [I b] and a compound represented by the general formula [I c], and the at least one hydrophilic colloid layer contains a polymer compound having a heterocycle substituted with a sulfonic acid group. A silver halide photographic material characterized by: (2) A method for processing a silver halide photographic material according to claim 1, which comprises processing the silver halide photographic material according to claim 1 within a processing time of 45 seconds from development, fixing, washing and/or stabilizing solution. . General formula [I a] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [I b] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [I c] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [Formula In the formula, R_1, R_2, R_3, R_4, R_5 and R_6 each represent an alkyl group, Y_1 and Y_2 represent a group of nonmetallic atoms necessary to form a pyrrolopyridine ring, and the ring of Y_1 has the formula ▲, There are chemical formulas, tables, etc.▼Including bonds, Y_2
In the ring ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼ shall include bonds. R_1, R_2, R_3, R in general formula [I a]
_4, R_5, R_6, Y_1, Y_2, general formula [I
R_1, R_2, R_3, R_4, R_5 in [b]
, R_6, Y_1, Y_2 and R_1, R_2, R_3, R_4, R_5, R_6 in general formula [I c],
Y_1, Y_2 are each a group that allows the dye molecule to have at least two acid groups or -CH_2CH_2
Represents a group capable of having at least two substituents having one or more OR groups. R represents a hydrogen atom or an alkyl group. L represents a methine group, and X^■ represents an anion. m represents an integer of 4 to 5, and n represents an integer of 1 or 2. When the dye forms an inner salt, n is 1. ]